Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation, and power source for sensor

Abstract

Provided are the following: a thermoelectric conversion element including, on a substrate, a first electrode, a thermoelectric conversion layer and a second electrode, in which the thermoelectric conversion layer contains an electroconductive nanomaterial having an average length in the major axis direction of at least 5 nm and a polymer compound having a repeating unit represented by the following Formula (1); an article for thermoelectric power generation and a power source for sensors, which use this thermoelectric conversion element; and a thermoelectric conversion material for forming the thermoelectric conversion layer, the thermoelectric conversion material containing the electroconductive nanomaterial described above and a polymer compound having a repeating unit represented by the following Formula (1). In Formula (1), ring A represents a conjugated hydrocarbon ring or a conjugated heterocyclic ring; X represents a group having one or two or more atoms selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, and a silicon atom, shared as ring-constituting atoms of the ring A; the average inter-unit distance of the ring A is 1.42 Å or less; R 11 and R 12 each independently represent a substituent, and may be bonded to each other to form a ring; and the symbol * represents a bonding position for the repeating unit.

What is claimed is: 
     
         1 . A thermoelectric conversion element comprising, on a substrate:
 a first electrode;   a thermoelectric conversion layer; and   a second electrode,   wherein the thermoelectric conversion layer contains an electroconductive nanomaterial having an average length in the major axis direction of at least 5 nm, and a polymer compound having a repeating unit represented by the following Formula (1), and   
       
         
           
           
               
               
           
         
         in Formula (1), ring A represents a conjugated hydrocarbon ring or a conjugated heterocyclic ring; X represents a group having one or two or more atoms selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom and a silicon atom, shared as ring-constituting atoms of the ring A; the average inter-unit distance of the ring A is 1.42 Å or less; R 11  and R 12  each independently represent a substituent, and may be bonded to each other to form a ring; and the symbol * represents a bonding position for the repeating unit. 
       
     
     
         2 . The thermoelectric conversion element according to  claim 1 ,
 wherein the polymer compound has a repeating unit represented by the following Formula (2), and   
       
         
           
           
               
               
           
         
         in Formula (2), ring B represents an aromatic ring; ring B may have a substituent, and may have an aromatic hydrocarbon ring or an aromatic heterocyclic ring fused thereto; rings A and X have the same meanings as the rings A and X of Formula (1) described above; the average inter-unit distance of the ring A is 1.42 Å or less; and the symbol * represents a bonding position for the repeating unit. 
       
     
     
         3 . The thermoelectric conversion element according to  claim 1 ,
 wherein the ring structure of the ring A is a ring structure represented by arty one of the following Formulae (3) to (8), and   
       
         
           
           
               
               
           
         
         in Formulae (3) to (8), each Y independently represents an atom selected from the group consisting of a carbon atom, a sulfur atom, a nitrogen atom, a phosphorus atom, and a silicon atom; two Y's in Formulae (7) and (8) may be identical or different; n represents an integer of 1 or more; RP represents an alkyl group or an aryl group; in a case in which n represents an integer of 2 or more in Formula (5), and in the case of Formula (6) and Formula (8), plural R's may be identical or different; and the symbol * represents a bonding position for the ring A. 
       
     
     
         4 . The thermoelectric conversion element according to  claim 2 , wherein the ring B is a benzene ring or a 5-membered or 6-membered aromatic heterocyclic ring. 
     
     
         5 . The thermoelectric conversion element according to  claim 1 , wherein the polymer compound has at least one repeating unit selected from the group consisting of an ethenylene group, an ethynylene group, an arylene group, and a heteroarylene group. 
     
     
         6 . The thermoelectric conversion element according to  claim 1 , wherein the thermoelectric conversion layer contains at least one polymer binder selected from a conjugated polymer binder and a non-conjugated polymer binder. 
     
     
         7 . The thermoelectric conversion element according to  claim 1 , wherein the electroconductive nanomaterial is a carbon nanomaterial or a metal nanomaterial. 
     
     
         8 . The thermoelectric conversion element according to  claim 1 , wherein the electroconductive nanomaterial is at least one material selected from the group consisting of carbon nanotubes, carbon nanofibers, graphite, graphene, carbon nanoparticles, and metal nanowires. 
     
     
         9 . The thermoelectric conversion element according to  claim 1 , wherein the electroconductive nanomaterial is the carbon nanotube. 
     
     
         10 . The electroconductive conversion element according to  claim 1 , wherein the thermoelectric conversion layer contains a dopant. 
     
     
         11 . The thermoelectric conversion element according to  claim 1 , wherein the substrate has flexibility. 
     
     
         12 . The thermoelectric conversion element according to  claim 1 , wherein the first electrode and the second electrode are each independently formed from aluminum, gold, silver, or copper. 
     
     
         13 . An article for thermoelectric power generation, using the thermoelectric conversion element according to  claim 1 . 
     
     
         14 . A power source for sensors, using the thermoelectric conversion element according to  claim 1 . 
     
     
         15 . A thermoelectric conversion material for forming a thermoelectric conversion layer of a thermoelectric conversion element,
 wherein the thermoelectric conversion material includes an electroconductive nanomaterial having an average length in the major axis direction of at least 5 nm, and a polymer compound having a repeating unit represented by the following Formula (1), and   
       
         
           
           
               
               
           
         
         in Formula (1) ring A represents a conjugated hydrocarbon ring or a conjugated heterocyclic ring; X represents a group having one or two or more atoms selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom and a silicon atom, shared as ring-constituting atoms of the ring A; the average inter-unit distance of the ring A is 1.42 Å or less; R 11  and R 12  each independently represent a substituent, and may be bonded to each other to form a ring; and the symbol * represents a bonding position for the repeating unit. 
       
     
     
         16 . The thermoelectric conversion material according to  claim 15 ,
 wherein the polymer compound has a repeating unit represented by the following Formula (2), and   
       
         
           
           
               
               
           
         
         in Formula (2), ring B represents an aromatic ring; ring B may have a substituent, and may have an aromatic hydrocarbon ring or an aromatic heterocyclic ring fused thereto; rings A and X have the same meanings as the rings A and X of Formula (1) described above; the average inter-unit distance of the ring A is 1.42 Å or less; and the symbol * represents a bonding position for the repeating unit. 
       
     
     
         17 . The thermoelectric conversion material according to  claim 16 , wherein the ring B is a benzene ring or a 5-membered or 6-membered aromatic heterocyclic ring. 
     
     
         18 . The thermoelectric conversion material according to  claim 15 , containing at least one polymer binder selected from a conjugated polymer binder and a non-conjugated polymer binder. 
     
     
         19 . The thermoelectric conversion material according to  claim 15 , containing an organic solvent. 
     
     
         20 . The thermoelectric conversion material according to  claim 19 , obtained by dispersing the electroconductive nanomaterial in the organic solvent.